CN114477217A - Ultrastable Y-type molecular sieve and preparation method and application thereof - Google Patents
Ultrastable Y-type molecular sieve and preparation method and application thereof Download PDFInfo
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- CN114477217A CN114477217A CN202011158172.3A CN202011158172A CN114477217A CN 114477217 A CN114477217 A CN 114477217A CN 202011158172 A CN202011158172 A CN 202011158172A CN 114477217 A CN114477217 A CN 114477217A
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 128
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 151
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000010555 transalkylation reaction Methods 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000011148 porous material Substances 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims description 39
- 238000001035 drying Methods 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 35
- 238000005406 washing Methods 0.000 claims description 35
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 27
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 239000007791 liquid phase Substances 0.000 claims description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 16
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 11
- 229910052731 fluorine Inorganic materials 0.000 claims description 11
- 239000011737 fluorine Substances 0.000 claims description 11
- 238000004537 pulping Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 150000003863 ammonium salts Chemical class 0.000 claims description 9
- 229910052593 corundum Inorganic materials 0.000 claims description 9
- 235000006408 oxalic acid Nutrition 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 238000011105 stabilization Methods 0.000 claims description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 229940070337 ammonium silicofluoride Drugs 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 10
- 238000007086 side reaction Methods 0.000 abstract description 5
- 238000009792 diffusion process Methods 0.000 abstract description 4
- 239000000376 reactant Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 description 27
- 238000010438 heat treatment Methods 0.000 description 22
- 238000010306 acid treatment Methods 0.000 description 21
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 20
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 15
- 238000005804 alkylation reaction Methods 0.000 description 12
- 238000012512 characterization method Methods 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 235000019270 ammonium chloride Nutrition 0.000 description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 229910021536 Zeolite Inorganic materials 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 239000012752 auxiliary agent Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 7
- 238000005342 ion exchange Methods 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 239000010457 zeolite Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 230000029936 alkylation Effects 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 238000003795 desorption Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 241000219782 Sesbania Species 0.000 description 4
- 241000219793 Trifolium Species 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 150000007524 organic acids Chemical group 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- VIDOPANCAUPXNH-UHFFFAOYSA-N 1,2,3-triethylbenzene Chemical compound CCC1=CC=CC(CC)=C1CC VIDOPANCAUPXNH-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000282346 Meles meles Species 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- -1 acid strength Chemical compound 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005360 mashing Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/20—Faujasite type, e.g. type X or Y
- C01B39/24—Type Y
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
-
- B01J35/617—
-
- B01J35/633—
-
- B01J35/635—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
- C07C2/66—Catalytic processes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses an ultrastable Y-type molecular sieve and a preparation method and application thereof. According to the ultrastable Y-type molecular sieve provided by the invention, the mesoporous volume accounts for more than 50% of the total pore volume; the amount of the strong B acid accounts for 40-70% of the total amount of the B acid. The ultrastable Y-type molecular sieve has the characteristics of high proportion of strong B acid and rich mesopores, can complete reaction at a lower reaction temperature when used for transalkylation reaction of benzene and polyalkylbenzene, can improve reactant diffusion, enhances the accessibility of activity, can reduce the occurrence of side reactions, and has good activity and selectivity.
Description
Technical Field
The invention relates to an ultra-stable Y-type molecular sieve, a preparation method and application thereof, wherein the Y-type molecular sieve can be used in a transfer reaction of diethylbenzene and benzene alkyl.
Background
Ethylbenzene is an important basic organic raw material, is mainly used for producing styrene, is an important monomer for synthesizing polystyrene, styrene-butadiene rubber, ABS, SBS and the like, is also applied to pharmaceutical industry, coating industry and textile industry, and has wide application.
Ethylbenzene is mainly synthesized by benzene and ethylene through alkylation reaction, in the alkylation reaction process of benzene and ethylene, because ethylbenzene which is a reaction product is continuously subjected to alkylation reaction with raw material ethylene to generate polyethylbenzene components such as diethylbenzene, triethylbenzene, tetra-ethylbenzene and the like, in order to improve the yield of ethylbenzene, polyethylbenzene materials are separated from the alkylation reaction products in industrial production, and then ethylbenzene is generated through transalkylation reaction. Up to now, the industrialized ethylbenzene production method is mainly AlC13Liquid phase alkylation, molecular sieve gas phase alkylation and molecular sieve liquid phase alkylation. Among the gas-phase alkylation processes, the ExxonMobil/Badger molecular sieve gas-phase alkylation process is in the lead of the world, only one reactor is adopted in the 1 st generation process and the 2 nd generation process, the gas-phase alkylation reaction of benzene and ethylene and the gas-phase transalkylation reaction of benzene and polyethylbenzene occur in the reactor, and with continuous research on the alkylation and transalkylation reactions, the 3 rd generation process adopts a single alkylation reactor and a single transalkylation reactor, and different catalysts are configured in a targeted manner. The disclosed liquid phase transalkylation process uses USY molecular sieve as active component of catalyst, and adopts water vapor treatment and SiCl respectively4The modification methods such as treatment or roasting treatment, etc. can greatly improve the performance of the catalyst, but still have the problems of high reaction temperature (above 190 ℃), more side reactions, high energy consumption of the device, short service life of the catalyst, etc.
As the advantages of low temperature reactions in liquid phase processes have become increasingly recognized by researchers, molecular sieve liquid phase transalkylation processes have been developed in succession. WO 91/18849 of Lummus company reports a liquid phase transalkylation reaction using zeolite or super acid as catalyst, at 170-270 deg.C and 400-600Pa, at a benzene-alkyl molar ratio of 3-10 and at a mass space velocity of 3-10 h-1. CN1323739A discloses that a Y-type molecular sieve is developed for use in polyethylbenzene and benzene transalkylation processes, the molecular sieve being prepared by at least one treatment step in an ammonia atmosphere at room temperature to 650 ℃ for 0.5-4h, preferably 150-600 ℃ for 1-3 h. US5371310 discloses the preparation of transalkylation catalysts using MCM-22 molecular sieves, MCM-22 being a layered microporous molecular sieve having an MWW structure, with improved diffusion properties of large reactant molecules in the micropores due to the presence of layer gaps. CN103030518A discloses that multi-stage pore beta zeolite is prepared by a dry glue conversion method and used as a diisopropylbenzene transalkylation catalyst, so that the activity stability of diisopropylbenzene is improved.
During the transalkylation reaction, the acid properties of the molecular sieve, including acid strength, acid amount and distribution thereof, are important parameters, and the control of the acid properties is an important index for modifying the performance of the USY molecular sieve. Great hessian and the like (great hessian, treighi, simple bud, excellent. Al and Bi grade P modified beta molecular sieve surface acidity and effect on transalkylation reaction [ J ] ion exchange and adsorption 1999, 15: 359 363.) Gao Tie Man and the like believe that (Gao Tie Man, Jia Tong, Qian, Liu Shang Yi, Wang Jing, research on transalkylation reaction of aromatic hydrocarbon on H beta zeolite [ J ] Petroleum institute (Petroleum processing), 1994, 10: 36-46.), distribution of catalyst strength influences the depth of transalkylation reaction. Therefore, the control of the acid property is an important index for modifying the performance of the USY molecular sieve.
In summary, the development of a Y-type molecular sieve with high acid strength and abundant mesopores is one of the problems to be solved in the art.
Disclosure of Invention
The invention aims to solve the technical problem of poor activity and selectivity of the low-temperature liquid-phase transalkylation catalyst in the prior art. The invention provides an ultra-stable Y-type molecular sieve and a preparation method and application thereof. The ultrastable Y-type molecular sieve has the characteristics of high proportion of strong B acid and rich mesopores, can complete reaction at a lower reaction temperature when used for transalkylation reaction of benzene and polyalkylbenzene, can improve reactant diffusion, enhances the accessibility of activity, can reduce the occurrence of side reactions, and has good activity and selectivity.
The invention provides an ultra-stable Y-type molecular sieve, wherein the medium pore volume of the ultra-stable Y-type molecular sieve accounts for more than 50% of the total pore volume; the amount of the strong B acid accounts for 40-70% of the total amount of the B acid; the specific surface area is 650-800m2Per g, pore volume of 0.45-0.65cm3(ii)/g; the mesoporous volume is 0.20-0.32 ml/g.
The medium pore volume of the ultrastable Y-shaped molecular sieve accounts for 50-75% of the total pore volume; the amount of the strong B acid accounts for 55 to 70 percent of the total amount of the B acid.
In the above technical scheme, the ultrastable Y-type molecular sieve is SiO of a framework2/Al2O3In the molar ratio of (12-27): 1.
in the above technical scheme, in the ultrastable Y-type molecular sieve, the total acid amount of B acid is 730-780 μmol/g, the amount of strong acid B is 420-500 μmol/g, the total acid amount of L acid is 450-750 μmol/g, and the amount of strong acid L is 350-550 μmol/g.
In the above technical scheme, in the ultrastable Y-type molecular sieve, the ratio of the total acid amount of the B acid to the total acid amount of the L acid is 0.8-1.8, preferably 1.2-1.8.
The second aspect of the invention provides a preparation method of the ultrastable Y-type molecular sieve, which comprises the following steps:
(1) adding fluorine-containing aqueous solution into ammonium fluosilicate solution, mixing with Y-type molecular sieve raw powder, washing, drying,
obtaining a pretreated Y-type molecular sieve;
(2) mixing the pretreated Y-type molecular sieve, ammonium salt and water, pulping, adding an acid solution A, stirring, washing and drying to obtain a sample;
(3) and (3) carrying out hydrothermal ultra-stabilization treatment on the sample obtained in the step (2), and drying to obtain the ultra-stable Y-type molecular sieve.
In the technical scheme, the concentration of the ammonium fluosilicate solution in the step (1) is 0.05-2 mol/L.
In the technical scheme, the Y-type molecular sieve raw powder adopted in the step (1) is SiO2And Al2O3The molar ratio of Si to Al is not less than 5.3, preferably not less than 5.5, butNot exceeding 10.0.
In the above technical scheme, the fluorine precursor compound in the fluorine-containing aqueous solution in step (1) is one selected from hydrofluoric acid, ammonium fluoride and ammonium bifluoride, and the molar ratio of fluorine element in the fluorine precursor compound to aluminum atoms in the Y-type molecular sieve is 0.005-0.5: 1, preferably 0.05-0.25: 1.
In the technical scheme, the mixture obtained in the step (1) is stirred for 10-60min at 40-80 ℃.
In the technical scheme, the Y-type molecular sieve, the ammonium salt and the water pretreated in the step (2) are prepared according to the following steps of: ammonium salt: water 1: (0.5-2): (5-20) mixing in a mass ratio; the pulping process in the step (2) is stirring exchange for 0.5-5h at 20-100 ℃, and the stirring exchange can be repeated for 1-3 times.
In the above technical solution, the acid solution a in the step (2) includes an inorganic acid, which may be one or a mixture of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid, carbonic acid, and citric acid.
In the technical scheme, the concentration of the acid solution A in the step (2) is 0.2-2 mol/L; in the step (2), the stirring process is to stir for 0.5 to 2 hours at the temperature of between 80 and 95 ℃.
In the technical scheme, deionized water is adopted for washing in the step (2), and drying is kept at the temperature of 100 ℃ and 130 ℃ for 10-15 h.
In the above technical scheme, the hydrothermal ultra-stabilization treatment process in step (3) comprises placing the sample in step (2) at 400-850 deg.C, and calcining in a steam atmosphere of 20-100% (by volume) for 0.5-10 h. The unit cell parameter of the molecular sieve after the hydrothermal treatment is 2.430-2.446 nm; wherein the constant temperature rise speed in the hydrothermal ultra-stabilization treatment process is 1-10 ℃/min.
In the technical scheme, the temperature for the hydrothermal hyperstabilization treatment in the step (3) is preferably 500-700 ℃, and the hydrothermal treatment is carried out for 1-4h by using 50-100% (volume) of water vapor.
In the above technical scheme, the drying in step (3) is maintained at 100-130 ℃ for 10-15 h.
The third aspect of the invention provides an application of the ultrastable Y-type molecular sieve in preparing ethylbenzene by transalkylation reaction.
As described aboveIn the technical scheme, the reaction pressure is 1.0-5.0MPa, and the weight space velocity of the liquid phase is 1.0-5.0h-1The reaction temperature is 140 ℃ and 190 ℃, and the benzene: the weight ratio of the polyethylbenzene is 1-5: 1. Preferably, the reaction temperature is 145-170 deg.C, more preferably 145-155 deg.C.
The invention provides an application of a low-temperature liquid-phase transalkylation catalyst obtained by the ultrastable Y-type molecular sieve and the binder in preparation of ethylbenzene through transalkylation reaction.
In the technical scheme, the low-temperature liquid-phase transalkylation catalyst comprises 50-99% of the ultrastable Y-type molecular sieve and 1-50% of a binder.
In the technical scheme, the reaction pressure is 1.0-5.0MPa, and the weight space velocity of the liquid phase is 1.0-5.0h-1The reaction temperature is 140 ℃ and 190 ℃, and the benzene: the weight ratio of the polyethylbenzene is 1-5: 1. Preferably, the reaction temperature is 145-170 deg.C, more preferably 145-155 deg.C.
In the technical scheme, the content of the binder is 10% -35%, wherein the binder is selected from at least one of alumina, silica, clay or diatomite.
The preparation method of the low-temperature liquid-phase transalkylation catalyst comprises the steps of treating the ultrastable Y molecular sieve by using an acid solution B; and then adding an auxiliary agent and a binder into the treated molecular sieve to prepare the low-temperature liquid-phase transalkylation catalyst.
In the above preparation method, the acid solution B is an organic acid or an inorganic acid, preferably an organic acid, and may be at least one of oxalic acid, citric acid, or acetic acid. The treatment with the acid solution B may be carried out one or more times. After the treatment with the acid solution B, ammonium ion exchange may be further performed, and one or more ammonium ion exchanges may be performed. The acid treatment step is carried out according to a conventional method in the field, wherein the mass ratio of the molecular sieve to the acid solution B is 1: 0.5-5 ℃, the treatment temperature is 50-100 ℃, and the pickling time is 0.5-3 h.
In the above-mentioned production method, the ammonium ion exchange method is well known to those skilled in the art, and the present invention is not particularly limited thereto. Specifically, the ammonium ion exchange process is as follows: mixing the modified Y molecular sieve with an ammonium salt solution for ammonium ion exchange, and adding an acidic solution in the exchange process to adjust the pH value to be within the range of 2.0-6.0. According to molecular sieve (dry basis): ammonium salt: water 1: (0.5-2): (5-20) pulping, and stirring and exchanging for 0.5-5h at 50-100 ℃. As in the conventional operation, the ammonium salt used in the ammonium exchange process may be one or more selected from ammonium sulfate, ammonium chloride, ammonium nitrate, ammonium acetate, ammonium oxalate, ammonium phosphate, etc. The acidic solution for adjusting the pH value of the system in the ammonium ion exchange process can be one or a mixture of more of aqueous solutions of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid, carbonic acid and the like.
In the preparation method, the molecular sieve, the alumina and the auxiliary agent are kneaded according to the weight ratio of 80-150: 15-40: 1.
In the preparation method, after the auxiliary agent and the binder are added into the treated molecular sieve, the drying and roasting steps are carried out, wherein the drying condition is drying at the temperature of 100-150 ℃. The roasting conditions include: the roasting temperature is 400-700 ℃; and/or the roasting time is 1-8 h.
The invention has the following beneficial effects:
1. the ultrastable Y-type molecular sieve provided by the invention has the characteristics of high proportion of strong B acid and rich mesopores, can realize reaction at a lower reaction temperature when used for transalkylation reaction of benzene and polyalkylbenzene, can improve reactant diffusion, enhances the accessibility of activity, can reduce the occurrence of side reaction, and has good activity and selectivity.
2. The preparation method of the ultrastable Y-type molecular sieve provided by the invention is characterized in that the Y-type molecular sieve is used as a raw material, a fluorine-containing aqueous solution is added into an ammonium fluosilicate solution, then the ammonium fluosilicate solution is mixed with the Y-type molecular sieve, and the USY molecular sieve catalyst with high acid strength and rich mesopores is prepared by combining acid solution A treatment and water vapor treatment, so that the USY molecular sieve catalyst with less skeleton collapse and complete molecular sieve crystal structure is prepared.
Drawings
FIG. 1 is a graph showing NH of USY type molecular sieves obtained in examples 1 and 2 and comparative example 13-a graph of the characterization results of the TPD;
FIG. 2 is a graph showing Py-IR characterization results at 200 ℃ for USY-type molecular sieves prepared in examples 1 and 2 and comparative example 1;
FIG. 3 is a graph showing Py-IR characterization results at 350 ℃ for USY-type molecular sieves prepared in examples 1 and 2 and comparative example 1;
FIG. 4 is an XRD diffractogram of USY type molecular sieves prepared in examples 1 and 2 and comparative example 1.
Detailed Description
In order that the present invention may be more readily understood, the following detailed description of the invention is given by way of example only, and is not intended to limit the scope of the invention.
It should be noted that the invention has been described with reference to an exemplary embodiment, but that the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
(1) The method for measuring the mesoporous volume and the total pore volume of the USY molecular sieve comprises the following steps: according to RIPP 151-90 standard method (compiled in "petrochemical analysis methods" (RIPP test methods), Yanggui, etc., published by scientific publishing company, 1990), the total pore volume of the molecular sieve is determined according to the adsorption isotherm, then the micropore volume of the molecular sieve is determined according to a T-plot method from the adsorption isotherm, and the mesopore volume is obtained by subtracting the micropore volume from the total pore volume. The specific surface area, the pore volume and the pore size distribution are measured by adopting a nitrogen adsorption-desorption isotherm, and the specific operation is as follows: the instrument model used was Micromeritics ASAP 2020 and the test temperature was-196 ℃. Before the nitrogen physisorption, the sample was degassed at 330 ℃ for 4h under 1.33 Pa.
(2) The relative crystallinity and the silicon-aluminum ratio are measured by adopting a Japan Shimadzu XRD6000 type X-ray powder diffractometer under the following test conditions: CuK α radiation, Ni filtering, tube voltage 30kV, tube current 40mA, step width 0.02, sample crystallinity (relative crystallinity) was calculated using the sum of the areas of eight peaks (compared to NaY molecular sieve standard) for (331), (511, 333), (440), (533), (642), (822, 660), (555, 751), and (664). The silica to alumina ratio was determined according to SH/T0339-92 (see "compilation of standards for chemical industry", published by Chinese standards Press, 2000) according to the following formula:
calculating the cell constant a
In the formula:
a-unit cell constant
λ—Cu-Kα1Wavelength of light
(h2+k2+l2) -sum of squares of X-ray diffraction indices.
And (3) calculating the silica-alumina ratio of the Y-type zeolite according to a Breck-Flanigen formula:
Si/Al＝(25.858-a)/(a-24.191)。
(3) acid strength by NH3TPD assay, in particular by: tabletting, mashing and screening the USY type molecular sieve, and drying 20-40 mesh particles for later use to obtain a sample to be detected. In the experiment, 0.15g of the dried sample to be tested was accurately weighed and placed in a quartz tube. The lower part of the zeolite bed layer is supported by a quartz sand bed layer, and the upper part of the zeolite bed layer is covered by the quartz sand bed layer, so that the zeolite bed layer is positioned at the position of a thermocouple. Heating the sample to 550 ℃ in He atmosphere, activating for 3h, cooling to room temperature, adsorbing 100% ammonia for 20min, heating to 100 ℃ for constancy, heating to 650 ℃ at the heating rate of 10 ℃/min when the baseline is stable, and collecting an ammonia desorption signal.
(4) The total acid amount of the B acid, the strong acid amount of the B acid and the total acid amount of the L acid are measured by pyridine infrared (Py-IR), and the specific operation is as follows: the sample is ground, dried and pressed into a sheet (15 mm of grinding tool). Absolute drying is guaranteed before weighing the sample. The sample was treated at 673K, 10-4Pretreating for 2 hours under Pa, cooling to room temperature, and sweeping 1300-1700 cm-1The ir spectrum of the range, saved as background. Adsorbing pyridine at room temperature, balancing the adsorption, vacuumizing, and removing the physically adsorbed pyridine molecules. Then the temperature is raised to the measuring temperature (200 ℃, 350 ℃) at 10 DEG C-4Desorbing for 1h under Pa, cooling to room temperature, and recording at 1300-1700 cm-1Infrared spectrum of the range. The L acid amount and the B acid amount of the sample are measured after desorption at 200 ℃ and are the total acid amounts of different acid strengths, and the strong L acid amount and the strong B acid amount of the sample after desorption at 350 ℃ are the sum of the medium strong acid amount and the strong acid amount.
Amount of acid adsorbed on pyridine c(B,L)The following can be obtained according to the formula:
εB＝0.059+0.004A
εL＝0.084+0.003A
c(B,L)＝A×g-1×ε(B,L) -1
in the formula, c(B,L)The number of B or L acid centers per gram of sample, and the unit of acid amount is mu. mol/g; a is the absorbance of the infrared spectrum; g is the mass of the sample per unit area, and the unit is g cm-2；ε(B,L)Is the extinction coefficient in cm2·μmol-1。
(5) The phase (XRD) of the USY samples was determined using a Bruker model D8X-ray powder diffractometer (Cu ka,
) And measuring by a scanning diffractometer. Cu target, graphite monochromatic filter, slit SS/DS 1 °, RS 0.15mm, operating voltage: 40KV, current: 30 mA.
(6) The diethylbenzene conversion rate is calculated according to formula 1, the ethylbenzene selectivity is calculated according to formula 2, and the heavy component yield is calculated according to formula 3.
The percent conversion of diethylbenzene is (weight of diethylbenzene in the starting material-weight of diethylbenzene in the product)/weight of diethylbenzene in the starting material x 100% (formula 1),
ethyl benzene selectivity ═ moles of ethyl benzene produced/(moles of benzene consumed + moles of diethylbenzene consumed) × 100% (equation 2),
the weight yield ═ weight (weight of weight in product)/total weight of product × 100% (formula 3).
[ example 1 ] A method for producing a polycarbonate
Adding 1.2g of HF into 150g of 0.2mol/L ammonium fluosilicate solution, stirring uniformly, adding 30g of SiO2/Al2O3Heating to 60 ℃ for stirring for 30min, then carrying out suction filtration, washing and drying to obtain the pretreated Y molecular sieve, wherein the Y molecular sieve is 5.8.
Dispersing 20g of the pretreated molecular sieve in 200g of 9 wt% (calculated as ammonium chloride) ammonium chloride aqueous solution, pulping and stirring, adding 1mol/L oxalic acid solution after 20min for acid treatment, wherein the acid treatment temperature is 90 ℃, and the acid washing time is 1 h; finally, washing the mixture by using 20 times of deionized water, and drying the mixture for 12 hours at the temperature of 120 ℃;
and then placing the mixture into a hydrothermal furnace, heating to 650 ℃, leading 100 volume percent of water vapor into the hydrothermal hyperstabilization treatment process at a constant speed and heating rate of 8 ℃/min, roasting the mixture for 2h, and drying the mixture for 12h at 120 ℃ to prepare the USY type molecular sieve, wherein the USY type molecular sieve is marked as a sample USY-A.
NH to USY-A3Characterization of TPD, Py-IR and XRD, the results are shown in FIGS. 1-4.
Physical parameters characterizing USY-A: the relative crystallinity was 94%; the molar ratio of framework silicon to aluminum is 16: 1; the acid content of the strong B acid is 460 mu mol/g; the total acid content of the B acid is 735 mu mol/g; the ratio of the total acid amount of the B acid to the total acid amount of the L acid is 1.5, and the acid amount characterization is shown in Table 1; specific surface area of 664m2(ii)/g; pore volume of 0.53cm3(ii)/g; the mesoporous volume is 0.29ml/g, and the mesoporous volume accounts for 55 percent of the total pore volume.
[ example 2 ]
Take 0.7g NH4F is added into 190g of 0.2mol/L ammonium fluosilicate solution, and after being evenly stirred, 36g of SiO is added2/Al2O3Heating to 80 ℃ for stirring for 15min, then carrying out suction filtration, washing and drying to obtain the pretreated Y molecular sieve, wherein the molecular sieve is a 5.4Y molecular sieve.
Dispersing 25g of the pretreated molecular sieve in 220g of ammonium sulfate aqueous solution with the concentration of 9 weight percent (calculated by ammonium chloride), pulping and stirring, adding 0.6mol/L of acetic acid solution after 20min for acid treatment, wherein the acid treatment temperature is 75 ℃, and the acid washing time is 1.5 h; finally, washing the mixture by using 20 times of deionized water, and drying the mixture for 12 hours at the temperature of 120 ℃; and then placing the mixture into a hydrothermal furnace, heating to 670 ℃, carrying out hydrothermal ultra-stabilization treatment at a constant speed and a heating rate of 5 ℃/min, introducing 80 volume percent of water vapor, roasting for 2h, and drying at 120 ℃ for 12h to prepare the USY type molecular sieve, wherein the USY type molecular sieve is marked as a sample USY-B.
NH to USY-B3Characterization of TPD, Py-IR and XRD, the results are shown in FIGS. 1-4.
Physical parameters characterizing USY-B: the relative crystallinity was 92%; the molar ratio of framework silicon to aluminum is 13: 1; the acid content of the strong B acid is 425 mu mol/g; the total acid content of the B acid is 749 mu mol/g; the ratio of the total acid amount of the B acid to the total acid amount of the L acid is 1.4, and the acid amount characterization is shown in Table 1; specific surface area of 652m2(ii)/g; pore volume of 0.51cm3(ii)/g; the mesoporous volume is 0.27ml/g, and the mesoporous volume accounts for 53 percent of the total pore volume.
[ example 3 ]
Adding 1.0g of HF into 165g of 0.2mol/L ammonium fluosilicate solution, stirring uniformly, adding 40g of SiO2/Al2O3Heating to 50 ℃ for 6.5Y-type molecular sieve, stirring for 1h, and then carrying out suction filtration, washing and drying to obtain the pretreated Y-type molecular sieve.
Dispersing 30g of the pretreated molecular sieve in 280g of ammonium nitrate aqueous solution with the concentration of 10 weight percent (calculated by ammonium chloride), pulping and stirring, adding 1.4mol/L of oxalic acid solution after 20min for acid treatment, wherein the acid treatment temperature is 90 ℃, and the acid washing time is 2 h; finally, washing the mixture by using 20 times of deionized water, and drying the mixture for 12 hours at the temperature of 120 ℃; and then placing the mixture into a hydrothermal furnace, heating to 630 ℃, keeping the constant heating speed of 10 ℃/min in the hydrothermal ultra-stabilization treatment process, introducing 100 volume percent of water vapor, roasting for 2h, and drying at 120 ℃ for 12h to prepare the USY type molecular sieve, wherein the USY type molecular sieve is marked as a sample USY-C.
NH by USY-C3Characterization of TPD, Py-IR and XRD, with results similar to those of FIGS. 1-4. Physical parameters characterizing USY-C: the relative crystallinity is 95%; the molar ratio of framework silicon to aluminum is 23: 1; the acid content of the strong B acid is 546 mu mol/g; total acid content of B acidIs 782 mu mol/g; the ratio of the total acid amount of the B acid to the total acid amount of the L acid is 1.3; the specific surface area is 683m2(ii)/g; pore volume of 0.54cm3(ii)/g; the mesoporous volume is 0.31ml/g, and the mesoporous volume accounts for 57 percent of the total pore volume.
[ example 4 ]
Adding 20g of the USY-A molecular sieve prepared in the example 1 into 20g of 0.29mol/L oxalic acid solution for acid washing treatment, wherein the acid treatment temperature is 50 ℃, the acid washing time is 1h, and finally washing with 20 times of deionized water and drying at 120 ℃ for 12 h; then weighing 15g (dry basis weight) of the USY-A molecular sieve after acid treatment, adding 4.3g (dry basis weight) of alumina, adding 0.175g of sesbania powder as an auxiliary agent, uniformly mixing, adding a proper amount of nitric acid aqueous solution for kneading, extruding with a clover orifice plate to form a catalyst, drying the catalyst at 120 ℃, roasting at 550 ℃ for 6 hours, and cooling to room temperature to obtain the catalyst which is marked as Cat-A.
[ example 5 ]
Adding 26g of the USY-A molecular sieve prepared in the example 1 into 33g of 0.40mol/L citric acid solution for acid washing treatment, wherein the acid treatment temperature is 60 ℃, the acid washing time is 1h, and finally washing with 20 times of deionized water and drying at 120 ℃ for 12 h; then weighing 19g (dry basis weight) of the USY-A molecular sieve after acid treatment, adding 5.2g (dry basis weight) of alumina, adding 0.188g of sesbania powder as an auxiliary agent, uniformly mixing, adding a proper amount of nitric acid aqueous solution, kneading, extruding with a clover orifice plate to form a catalyst, drying the catalyst at 120 ℃, roasting at 550 ℃ for 5 hours, and cooling to room temperature to obtain the catalyst which is marked as Cat-B.
Comparative example 1
Taking 30g of SiO2/Al2O3Adding 5.8Y-type molecular sieve into 150g of 0.2mol/L ammonium fluosilicate solution, uniformly stirring, heating to 60 ℃, stirring for 30min, and then carrying out suction filtration, washing and drying to obtain the pretreated Y-type molecular sieve.
Dispersing 20g of the pretreated molecular sieve in 200g of ammonium sulfate aqueous solution with the concentration of 15 wt% (calculated by ammonium chloride), pulping and stirring, adding 0.5mol/L oxalic acid solution after 20min for acid treatment, wherein the acid treatment temperature is 90 ℃, and the acid washing time is 1 h; finally, washing the mixture by using 20 times of deionized water, and drying the mixture for 12 hours at the temperature of 120 ℃; and then placing the mixture into a hydrothermal furnace, heating to 670 ℃, carrying out hydrothermal ultra-stabilization treatment at a constant speed and a heating rate of 3 ℃/min, introducing 100 volume percent of water vapor, roasting for 2h, and drying at 120 ℃ for 12h to prepare the USY type molecular sieve, wherein the USY type molecular sieve is marked as a sample USY-D.
NH to USY-D3Characterization of TPD, Py-IR and XRD, the results are shown in FIGS. 1-4.
Wherein, the XRD spectrogram shows that the characteristic peak intensities USY-A and USY-B molecular sieves of faujasite with FAU structure are larger than USY-D, which shows that the framework collapse is less and the crystal structure of the molecular sieve is complete.
Physical parameters characterizing USY-D: the relative crystallinity was 88%; the molar ratio of the framework silicon to the aluminum is 10: 1; the acid content of the strong B acid is 389 mu mol/g; the total acid content of B acid is 719 mu mol/g; the ratio of the total acid amount of the B acid to the total acid amount of the L acid is 0.9, and the acid amount characterization is shown in Table 1; the specific surface area is 641m2(ii)/g; pore volume of 0.49cm3(ii)/g; the mesoporous volume is 0.24ml/g, and the mesoporous volume accounts for 49 percent of the total pore volume.
Comparative example 2
Taking 45g of SiO2/Al2O3Adding 7.2Y-type molecular sieve into 190g of 0.2mol/L ammonium fluosilicate solution, uniformly stirring, heating to 75 ℃, stirring for 50min, and then carrying out suction filtration, washing and drying to obtain the pretreated Y-type molecular sieve.
Dispersing 35g of the pretreated molecular sieve in 310g of 9 wt% (calculated as ammonium chloride) ammonium chloride aqueous solution, pulping and stirring, adding 0.8mol/L citric acid solution after 20min for acid treatment, wherein the acid treatment temperature is 80 ℃, and the acid washing time is 1.2 h; finally, washing the mixture by using 20 times of deionized water, and drying the mixture for 12 hours at the temperature of 120 ℃; and then placing the mixture into a hydrothermal furnace, heating to 650 ℃, leading 75 volume percent of water vapor into the hydrothermal hyperstabilization treatment process at a constant speed and at a heating rate of 7 ℃/min, roasting the mixture for 2h, and drying the mixture for 12h at 120 ℃ to prepare the USY type molecular sieve which is marked as a sample USY-E.
Physical parameters characterizing USY-E: the relative crystallinity was 86%; the molar ratio of framework silicon to aluminum is 17: 1; the acid content of the strong B acid is 395 mu mol/g; the total acid content of the B acid is 748 mu mol/g; the ratio of the total acid amount of the B acid to the total acid amount of the L acid is 1.0; specific surface area of 635m2(ii)/g; pore volume of 0.48cm3(ii)/g; the mesoporous volume is 0.25ml/g, and the mesoporous volume accounts for 52 percent of the total pore volume.
Comparative example 3
58g of SiO are taken2/Al2O3Adding 11.4 of Y-type molecular sieve into 167g of 0.3mol/L ammonium fluosilicate solution, uniformly stirring, heating to 60 ℃, stirring for 60min, and then carrying out suction filtration, washing and drying to obtain the pretreated Y-type molecular sieve.
Dispersing 35g of pretreated molecular sieve in 300g of 9 wt% (calculated as ammonium chloride) ammonium chloride aqueous solution, pulping and stirring, adding 0.5mol/L citric acid solution after 20min for acid treatment, wherein the acid treatment temperature is 60 ℃, and the acid washing time is 2 h; finally, washing the mixture by using 20 times of deionized water, and drying the mixture for 12 hours at the temperature of 120 ℃; and then placing the mixture into a hydrothermal furnace, heating to 600 ℃, carrying out hydrothermal ultra-stabilization treatment at a constant speed and a heating rate of 2 ℃/min, introducing 100 volume percent of water vapor, roasting for 2.5h, and drying at 120 ℃ for 12h to prepare the USY type molecular sieve, wherein the USY type molecular sieve is marked as a sample USY-F.
Physical parameters characterizing USY-F: the relative crystallinity was 84%; the molar ratio of framework silicon to aluminum is 19.8: 1; the acid content of the strong B acid is 379 mu mol/g; the total acid amount of the B acid is 701 mu mol/g; the ratio of the total acid amount of the B acid to the total acid amount of the L acid is 0.95; specific surface area of 592m2(ii)/g; pore volume of 0.46cm3(iv) g; the mesoporous volume is 0.20ml/g, and the mesoporous volume accounts for 43 percent of the total volume.
Comparative example 4
Adding 22g of the USY-D molecular sieve prepared in the comparative example 1 into 25g of 0.50mol/L oxalic acid solution for acid washing treatment, wherein the acid treatment temperature is 80 ℃, the acid washing time is 1.5h, and finally washing with 20 times of deionized water and drying at 120 ℃ for 12 h; then weighing 13g (dry basis weight) of the USY-D molecular sieve after acid treatment, adding 3.2g (dry basis weight) of alumina, adding 0.118g of sesbania powder as an auxiliary agent, uniformly mixing, adding a proper amount of nitric acid aqueous solution for kneading, extruding with a clover orifice plate to form a catalyst, drying the catalyst at 120 ℃, roasting at 550 ℃ for 5 hours, and cooling to room temperature to obtain the catalyst which is marked as Cat-C.
Comparative example 5
Adding 35g of the USY-E molecular sieve prepared in the comparative example 1 into 40g of 0.33mol/L acetic acid solution for acid washing treatment, wherein the acid treatment temperature is 90 ℃, the acid washing time is 2.0h, and finally washing with 20 times of deionized water and drying at 120 ℃ for 12 h; then 22g (dry basis weight) of the USY-E molecular sieve after acid treatment is weighed, 5.8g (dry basis weight) of alumina is added, 0.202g of sesbania powder as an auxiliary agent is added, a proper amount of nitric acid aqueous solution is added after the mixture is uniformly mixed and kneaded, the mixture is extruded by a clover orifice plate to form a catalyst, the catalyst is dried at 120 ℃, the catalyst is roasted at 550 ℃ for 5 hours, and the catalyst is cooled to room temperature, and the obtained catalyst is marked as Cat-D.
[ test example 1 ]
This example illustrates the evaluation of the initial activity of the inventive and comparative catalysts for the liquid phase transalkylation of benzene and polyethylbenzene.
The catalysts of examples 1 to 5 and comparative examples 1 to 4 were examined for reactivity with a fixed bed reactor from the bottom up, which was a stainless steel tube having an inner diameter of 28mm and a length of 800 mm. SO4 2-/ZrO2The loading of the Y-type catalyst was 3g and diluted to 10mL with glass beads. Respectively filling USY-A, USY-B, USY-C, USY-D, USY-E, Cat-A, Cat-B, Cat-C, Cat-D catalyst into a reactor, activating the catalyst under the protection of nitrogen, activating for 1h at 400 ℃, then cooling to room temperature, stopping nitrogen purging, starting to feed alkyl transfer material, and when the pressure reaches 3MPa, starting to heat to the reaction temperature. The reaction conditions are as follows: the temperature is 150 ℃, the reaction pressure is 3MPa, and the total liquid phase space velocity is 3.3h-1The weight ratio of benzene to polyethylbenzene is 1.8: 1, the evaluation results are shown in Table 1, in which the conversion and the selectivity are stable data for the initial 12h of feed. The results are shown in Table 2.
TABLE 1 acid characterization of USY-A, USY-B and USY-D molecular sieves
In connection with the context of FIG. 2, at 1540cm-1And 1450cm-1Here, the characteristic vibration peaks are respectively adsorbed on the B acid and the L acid. Table 1 lists the B and L acid acids of each USY molecular sieve at 200 ℃ and 350 ℃Volume data. It is generally considered that the L acid amount and the B acid amount of the sample measured after desorption at 200 ℃ are the total acid amounts of different acid strengths, and the strong L acid amount and the strong B acid amount of the sample after desorption at 350 ℃ are the sum of the medium strong acid amount and the strong acid amount. As can be seen from table 1, all USY molecular sieves contain a B acid center and an L acid center. The transalkylation reactivity depends on the number and strength of strong B acid centers. The USY-A and USY-B molecular sieves with the strong B acid content are larger than the USY-D, so that more strong B acid centers of the USY-A and the USY-B molecular sieves provide sufficient active sites for reaction.
TABLE 2 catalytic Properties of the examples and comparative examples
| Catalyst and process for preparing same | Diethylbenzene conversion% | Ethyl benzene selectivity,% | Heavy fraction of% |
| USY-A | 61 | 99.8 | 0.12 |
| USY-B | 64 | 99.7 | 0.11 |
| USY-C | 63 | 99.5 | 0.12 |
| USY-D | 48 | 98.2 | 0.16 |
| USY-E | 49 | 98.1 | 0.17 |
| USY-F | 46 | 97.5 | 0.17 |
| Cat-A | 59 | 99.0 | 0.13 |
| Cat-B | 61 | 99.2 | 0.13 |
| Cat- |
40 | 97.2 | 0.19 |
| Cat-E | 42 | 97.1 | 0.20 |
From the results of examples and comparative examples, fig. 1, fig. 2, fig. 3, and tables 1 and 2, it can be seen that the transalkylation catalyst obtained by the preparation method of the present invention has a high amount of strong B acid and rich mesopores. The catalyst has higher activity and larger product selectivity when being used for the transalkylation reaction of polyethylbenzene and benzene, and finally, the product distribution is optimized, and the occurrence of side reactions is reduced.
Claims (13)
1. An ultra-stable Y-type molecular sieve, wherein the medium pore volume of the ultra-stable Y-type molecular sieve accounts for more than 50% of the total pore volume; the amount of the strong B acid accounts for 40-70% of the total amount of the B acid; the specific surface area is 650-800m2Per g, total pore volume of 0.45-0.65cm3(ii)/g; the mesoporous volume is 0.20-0.32 ml/g.
2. The ultrastable Y-type molecular sieve of claim 1, wherein the SiO of the framework of the ultrastable Y-type molecular sieve2/Al2O3In the molar ratio of (12-27): 1.
3. the ultrastable Y-type molecular sieve of claim 1, wherein the total acid amount of the B acid in the ultrastable Y-type molecular sieve is 780 μmol/g, the total acid amount of the strong B acid is 500 μmol/g, the total acid amount of the L acid is 750 μmol/g and the total acid amount of the strong L acid is 550 μmol/g, wherein the total acid amount of the B acid is 730-.
4. The ultrastable Y-type molecular sieve of claim 1, wherein the ratio of total acid B to total acid L in the ultrastable Y-type molecular sieve is 0.8 to 1.8.
5. A process for the preparation of the ultrastable Y-type molecular sieve of any one of claims 1 to 4, comprising the steps of:
(1) adding a fluorine-containing aqueous solution into an ammonium fluosilicate solution, then mixing with Y-type molecular sieve raw powder, and washing and drying to obtain a pretreated Y-type molecular sieve;
(2) mixing the pretreated Y-type molecular sieve, ammonium salt and water, pulping, adding an acid solution A, stirring, washing and drying to obtain a sample;
(3) and (3) carrying out hydrothermal ultra-stabilization treatment on the sample obtained in the step (2), and drying to obtain the ultra-stable Y-type molecular sieve.
6. The production method according to claim 5, wherein the concentration of the ammonium silicofluoride solution in the step (1) is 0.05 to 2 mol/L; in the step (1), the fluorine precursor compound in the fluorine-containing aqueous solution is at least one of hydrofluoric acid, ammonium fluoride and ammonium bifluoride, and the molar ratio of fluorine element in the fluorine precursor compound to aluminum atoms in the Y-type molecular sieve is 0.005-0.5: 1, preferably 0.05-0.25: 1.
7. The method according to claim 5, wherein the Y-type molecular sieve, the ammonium salt and the water pretreated in the step (2) are as follows on a dry basis according to the Y-type molecular sieve: ammonium salt: water 1: (0.5-2): (5-20) mixing in a mass ratio; the pulping process in the step (2) is stirring exchange for 0.5-5h at 20-100 ℃, and the stirring exchange is repeated for 1-3 times.
8. The method according to claim 5, wherein the acid solution A in the step (2) comprises an inorganic acid selected from one or more mixed solutions of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid, carbonic acid, and citric acid; the concentration of the acid solution A in the step (2) is 0.2-2 mol/L; in the step (2), the stirring process is to stir at 80-95 ℃ for 0.5-2 h.
9. The preparation method as claimed in claim 5, wherein the hydrothermal ultra-stabilization treatment process in step (3) comprises placing the sample in step (2) at 400-850 ℃ and calcining in an atmosphere of water vapor with a volume concentration of 20-100% for 0.5-10 h.
10. Use of the ultrastable Y-type molecular sieve of any one of claims 1-4 in the transalkylation reaction to produce ethylbenzene.
11. Use of a low temperature liquid phase transalkylation catalyst comprising an ultrastable Y-type molecular sieve according to any one of claims 1-4 and a binder for the transalkylation reaction to produce ethylbenzene.
12. The use of claim 11, wherein the low temperature liquid phase transalkylation catalyst comprises 50% -99% of the ultrastable Y-type molecular sieve with 1% -50% of a binder.
13. Use according to claim 11 or 12, wherein the reaction pressure is 1.0-5.0MPa and the weight space velocity of the liquid phase is 1.0-5.0h-1The reaction temperature is 140 ℃ and 190 ℃, and the reaction temperature is benzene: the weight ratio of the polyethylbenzene is 1-5: 1; preferably, the reaction temperature is 145-170 deg.C, more preferably 145-155 deg.C.
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